(2S,3R)-2-<(benzyloxy)methoxy>-3-<(tert-butyldimethylsilyl)oxy>-2-methylpentanal | 133782-37-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S,3R)-2-<(benzyloxy)methoxy>-3-<(tert-butyldimethylsilyl)oxy>-2-methylpentanal
• 英文别名: (2R,3R)-3-[tert-butyl(dimethyl)silyl]oxy-2-methyl-2-(phenylmethoxymethoxy)pentanal
• CAS: 133782-37-3
• 化学式: C₂₀H₃₄O₄Si
• 分子量: 366.573
• InChiKey: CSTQEKDSLPDPKX-QUCCMNQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.94
• 重原子数：
  25.0
• 可旋转键数：
  10.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  44.76
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (2S,3R)-2-<(benzyloxy)methoxy>-3-<(tert-butyldimethylsilyl)oxy>-2-methylpentanal 在 正丁基锂 、 邻苯二甲酸二甲酯 、 D(+)-10-樟脑磺酸 、 四丁基氟化铵 、 氨 、 sodium 、 lithium tri-t-butoxyaluminum hydride 、 六甲基二硅氮烷 作用下， 以 乙醚 为溶剂， 反应 6.25h， 生成 (2R,3R)-2-((4S,5R,6R)-6-{(1R,3R)-3-Hydroxy-1-methyl-3-[(4R,5S,6R)-2,2,5-trimethyl-6-((S)-1-methyl-allyl)-[1,3]dioxan-4-yl]-butyl}-2,2,5-trimethyl-[1,3]dioxan-4-yl)-pentane-2,3-diol
  参考文献：
  名称：

  Stereocontrolled synthesis of erythronolides A and B in A (C5-C9) + (C3-C4) + (C1-C2) + (C11-C13) sequence from 1,6-anhydro-β-D-glucopyranose (levoglucosan). Part 2.

  摘要：

  Stereocontrolled synthesis of erythronolides A and B has been achieved.

  DOI：

  10.1016/s0040-4020(01)96140-x
• 作为产物：
  描述：

  (1R,2S,3R,5R)-2-Allyloxy-3-benzyloxymethoxy-6,8-dioxa-bicyclo[3.2.1]octane 在 吡啶 、 咪唑 、 盐酸 、 sodium hydroxide 、 N-溴代丁二酰亚胺(NBS) 、 lithium aluminium tetrahydride 、 草酰氯 、 二甲基硫 、 邻苯二甲酸二甲酯 、 camphor-10-sulfonic acid 、 potassium tert-butylate 、 mercury(II) diacetate 、 双氧水 、 三乙基硼氢化锂 、 臭氧 、 二甲基亚砜 、 三乙胺 、 N,N-二异丙基乙胺 、 三苯基膦 、 三氟乙酸 、 锌 作用下， 以 四氢呋喃 、 甲醇 、 六甲基磷酰三胺 、 乙醚 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 异丙醇 为溶剂， 反应 39.17h， 生成 (2S,3R)-2-<(benzyloxy)methoxy>-3-<(tert-butyldimethylsilyl)oxy>-2-methylpentanal
  参考文献：
  名称：

  从1.6-脱水-β-D-葡萄糖醛酸（左旋葡聚糖）以（C5-C9）+（C3-C4）+（C1-C2）+（C11-C13）序列立体控制赤藓醇内酯A和B的合成。第1部分。C1-C10和C11-C13段的合成

  摘要：

  讨论了大环内酯类抗生素红霉素A和B的糖苷配基的合成方法，并描述了从左葡糖烷开始制备常​​见的C1-C10和C1-C13片段。

  DOI：

  10.1016/s0040-4020(01)96139-3

文献信息

• Strategies for Macrolide Synthesis. A Concise Approach to Protected Seco-Acids of Erythronolides A and B
  作者：Stephen F. Martin、Wen-Cherng Lee、Gregory J. Pacofsky、Ricky P. Gist、Thomas A. Mulhern

  DOI：10.1021/ja00090a016

  日期：1994.6

  Concise syntheses of protected derivatives of the seco-acids of erythronolides A and B, 5 and 6, respectively, have been completed wherein the longest linear sequence requires only 13 chemical steps from 5-ethylfuraldehyde (15). The syntheses commenced with the asymmetric aldol condensation of 15 according to the Evans protocol to afford the optically pure syn adduct 16, thereby establishing the critical stereocenters at C(4) and C(5) of the erythromycin backbone. Reductive removal of the chiral auxiliary from 16 gave the diol 17, which was converted to the bicyclic enone 18 by an one-pot process involving sequential oxidation of the furan ring and acid-catalyzed bicycloketalization. Stereoselective elaboration of 18 to the tertiary alcohol 19 was achieved in two steps by sequential treatment with lithium dimethylcuprate and methyllithium in the presence of cerium trichloride. Compound 19 underwent facile acid-catalyzed reorganization to the isomeric ketal 21, which was transformed into 24 by a Swern oxidation and a second asymmetric aldol condensation. However, the necessary refunctionalization of 24 into a ketone that would participate in the requisite aldol reaction to append the C(11)-C(15) segment of the erythronolide backbone could not be induced. On the other hand, transthioketalization of 19 gave the triol 26, which was converted to 28 by the thermodynamically-controlled formation of an acetonide of the 1,2-diol array. Deprotection of the C(9) ketone function followed by Swern oxidation produced the keto aldehyde 31, which underwent chemoselective, Lewis acid-mediated addition of tri-n-butylcrotylstannane to the aldehyde function to furnish a mixture (4:1) of the homoallylic alcohols 32 and 33; the major product 32 comprises the C(1)-C(10) subunit common to the seco-acids of both erythronolides A and B. Diastereoselective aldol condensation of the enolate derived from 32 with 40 gave 42 as the major adduct; oxidative processing of the terminal olefin then delivered the erythronolide B seco-acid derivative 46. The proposed structure of 42 was initially based upon its conversion into the polyol 48, which was identical to that derived from natural erythronolide B (49). Subsequent to this chemical correlation, the X-ray structure of 50, which was prepared from 42, unequivocally verified this assignment. In experiments directed toward the preparation of the seco-acid of erythronolide A, the directed aldol reactions of 32 with the aldehydes 59 and 60 were examined. Although the addition of the enolate of 32 to 59 produced none of the requisite adduct, its reaction with 60 gave a mixture (1:5) of 62 and 64. Stereoselective reduction of the C(9) carbonyl function of 62 followed by oxidative cleavage of the double bond and global deprotection gave the polyol 62, which was identical with the polyol derived from natural erythromycin A (1).